Composition and method for dyeing keratinous fibers

ABSTRACT

Diphenylamines having the formula   WHEREIN: Y represents a member selected from the group consisting of a hydroxy and amino, R1 and R3, each independently, represent a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, a ureido residue, and -NHCOR wherein R is lower alkyl, R2 represents a member selected from the group consisting of hydrogen, halogen, lower alkyl, lower alkoxy, a ureido residue, -NHCOR wherein R is lower alkyl, and -NHR8 wherein R8 represents a member selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl and carbamylmethyl, with the proviso that when R2 is -NHR8, R3 is not hydrogen R4, R5, R6, and R7 each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy, with the proviso that when Y is hydroxy, R2 is not hydrogen, halogen, lower alkyl or lower alkoxy, and that when Y is amino, at least two of R1, R2 and R3 are other than a hydrogen and R2 is not hydrogen when R4, R5, R6 and R7 are all hydrogen and the acid addition salts of said diphenylamines.

United States Patent [191 Kalopissis et a1.

[4 1 Sept. 16, 1975 COMPOSITION AND METHOD FOR DYEING KERATINOUS FIBERS[75] Inventors: Gregoire Kalopissis, Paris; Andree Bugaut,Boulogne-sur-Seine; Francoise Estradier, Paris, all of France [73]Assignee: Societe Anonyme dite: LOreal, Paris, France [22] Filed: Oct.30, 1972 [21] Appl. No.: 301,998

Related US. Application Data [62] Division of Ser. No. 61,833, Aug. 6,1970, Pat. No.

8/11; 8/32; 260/396 N; 260/571; 260/573; 424/D1G. 2; 424/70; 424/71;8/11; 8/32 Primary Examiner-Stanley .1. Friedman Assistant Examiner-DaleR. Ore

Attorney, Agent, or Firm-Cushman, Darby & Cushman 57 ABSTRACTDiphenylamines having the formula wherein: Y represents a memberselected from the group consisting of a hydroxy and amino, R and R eachindependently, represent a member selected from the group consisting ofhydrogen, halogen, lower alkyl, lower alkoxy, a ureido residue, and-N1-1COR wherein R is lower alkyl, R represents a member selected fromthe group consisting of hydrogen, halogen,

lower alkyl, lower'alkoxy, a ureido residue, N1-1COR wherein R is loweralkyl, and -l 11-1R wherein R represents a member selected from thegroup consisting of hydrogen, lower alkyl, lower hydroxyalkyl andcarbamylmethyl, with the proviso that when R is NHR,,, R is not hydrogenR R R and R each independently represent a member selected from thegroup consisting of hydrogen, halogen, lower alkyl and lower alkoxy,with the proviso that when Y is hydroxy, R is not hydrogen, halogen,lower alkyl or lower alkoxy, and that when Y is amino, at least two of RR and R are other than a hydrogen and R is not hydrogen when R R R and Rare all hydrogen and the acid addition salts of said diphenylamines.

6 Claims, No Drawings COMPOSITION AND. METHOD FOR DYEING KERATINOUSFIBERS This is a division of application Ser. No. 61 ,833, filed Aug. 6,1970, now US. Pat. No. 3,792,090.

This invention relates to novel diphenylamines and a process forpreparing the sameand to novel cosmetic composition containingdiphenylamines for dyeing keratinic fibers such as human hair. Morespecifically, the present invention relates to a method and a use of anovel diphenylamine having the formula:

wherein: Y represents a member selected from the group consisting ofhydroxy and amino, R and R each independently, represent a memberselected from the group consisting of hydrogen, halogen, lower alkyl,lower alkoxy, ureido residue and --NHCOR group wherein R representslower alkyl, R represents a member selected from the group consisting ofhydrogen,

halogen, a lower alkyl, lower alkoxy, a ureido residue,

NHCOR wherein R represents lower alkyl and -NHR wherein R represents amember selected from the group consisting of hydrogen, a lower alkyl,lower hydroxy alkyl and carbamylmethyl, with the proviso that when R isNHR R is not hydrogen, R R R R each represent a member selected from thegroup consisting of hydrogen, halogen, lower alkyl, lower alkoxy, withthe proviso that when Y is hydroxy, R is not hydrogen, halogen, loweralkyl, or lower alkoxy radical, and that when Y is amino, at least twoof the radicals R R and R are other than hydrogenand R is not hydrogenwhen R R R R are all hydrogen, and the addition of salts of saiddiphenylamines with organic or inorganic acids.

In the above definition the terms lower alkyl and lower alkoxy radicalsdesignate groups containing from 1 to 4 carbon atoms. H

The diphenylamines of the present invention can be prepared by reducingan indoaniline or an indophenol having the formula wherein R R R R R R5,R and Y have the meanings given above in an alkaline medium having a pHranging from about 9 to 12, and in the presence of effective amounts ofa reducing agent selected from the group consisting of sodiumhydrosulfite or an alkaline sulfide such as sodium or ammonium sulfide.The amount of reducing agent can vary but generally it will be presentin amounts such that the mole ratio of indoaniline or indophenol beingreduced to reducing agent ranges between 1:1.5 to 1:3. The reducingreaction is generally carried out at ambient pressure and at atemperature ranging from about 25 to 50C.

The leucoderivatives of the present invention are colorless compoundswhich when applied in an aqueous medium to the fibers to be dyed,oxidize in the air or in the presence of added oxidizing agent, therebyyielding the corresponding indoanilines or indophenols, which arecolored compounds and which are directly responsible for the coloring ofthe keratinic fibers. An important advantage of these leucoderivativesover their corresponding oxidation products are their increasedsolubility in an aqueous medium and hence their greater fiberpenetrating characteristics. Because of these properties a betterquality and a greater intensity of fiber coloring is attainable.

The applicants have also found that these diphenylamineleucoderivatives, as well as known diphenylamines of closely relatedstructure, are advantageously employed in the preparation of capillaryhair-setting lotions. Consequently, the present invention also has forits object the provision of a capillary hair-setting 10- tion,characterized by the fact that it contains in dilute lower alkanolsolution having a titer ranging from about 50 to at least one cosmeticresin and at least one compound having the formula:

wherein Y, R, R R R R and R have the meaning indicated above, and Rrepresents a member selected from the group consisting of hydrogen,halogen, lower alkyl, lower alkoxy group, a ureido residue, NHCORwherein R represents lower alkyl, and NHR wherein R represents a memberselected from the group consisting of hydrogen, lower alkyl, lowerhydroxy alkyl and carbamylmethyl.

Representative cosmetic resins usefully employed in the presentinvention include polyvinylpyrrolidone having a molecular weight rangingfrom'about 10,000 to 700,000, copolymers of crotonic acid-vinyl acetate,copolymers of vinylpyrrolidone-vinyl acetate wherein the ratio of VP toVA can range for instance between 50-70:5030, copolymers of maleicanhydridebutylvinyl ether, and the like. These resins are generally usedin the proportion of l to 3% by weight of the total composition.

The alcohols suitable for making said hair-setting lotions are loweralkanols, preferably ethanol or isopropanol. These alcohols are used ina proportion of 20 to 50% by weight of the total composition.

The hair-setting lotions according to the invention contain from 0.01 to0.1% by weight of the diphenylamine leucoderivatives defined above, andhave a pH 1 between 7 and 10, and preferably between 7 and 9. The

pH can be obtained by adding to the lotion an alkaline agent such asammonia or triethanolamine.

The hair-setting lotion according to the invention is employedin aconventional manner by applying the same to previously washed and rinsedwet hair followed by rolling the treated hair on curlers and thereafterdrying it.

The hair-setting lotions of the present invention make it possible toimpart to the hair a remarkable coloring characterized by its uniformityand its brightness, without it being necessary to take particularprecautions and regardless of the degree of sensitivity of the hairbeing treated.'ln particular, in the case of irregularly bleached hairthe hair-setting lotions of this invention'make it possible to obtainresults that are quite hard to achieve by standard dyeing processes.

The coloring of the hair obtained, in addition to its qualities ofuniformity and brightness, is also characterized by glints which is anadditional quality highly prized byhair dyers.

Further, the hair-setting lotions of the present invention can alsocontain known leucoderivatives, particularly leucoderivatives ofindamines.

The following examples are given to illustrate the present invention.Unless otherwise specified all parts and percentages are by weight.

EXAMPLE 1 3 ,5-dimethyl-4-hydroxy-4 '-amino-3 ,5 '-dimethy1-2methoxy-diphenylamine is prepared according to the following reaction:

CH OCH 3 To 750 cm of a normal NaOH solution containing 73 g (0.35 mole)of sodium hydrosulfite, there is added, little by little, with stirringand under a nitrogen atmosphere, 0.1 mole (28.4 g) of N-[(4-amino-3',5'-dimethyl-2 -methoxy )phenyl] 2 ,6-dimethyl-- benzoquinoneimine insolution in 300 cm of ethyl a1- cohol, while keeping the temperature ofthe reaction mixture in the vicinity of 30C. When the reduction reactionis completed the reaction mass is rapidly fil-- 10 tered. The filtrateis cooled and neutralized with acetic OCH acid. 27 g of the abovediphenylamine leucoderivative is filtered which, after washing withwater and drying under a vacuum, exhibits a melting point of 137C.

Molecular mass calculated for C I-1 N 0 286. Molecular mass found bypotentiometric dosing in acetic acid by perchloric acid 291.

Calculated for Found n zz z z 9.78

Analysis 25 methoxy-diphenylamine is prepared according to the followingreaction: 7

orr

To cm of a normal NaOH solution containing 3.5 g (0.016 mole) of sodiumhydrosulfite, there is added, with stirring and under a nitrogenatmosphere, 0.005

mole (1.42 g) of N-[(4-amino-3',5'-dimethyl-2'-methoxy)phenyl12,5dimethyl-benzoquinoneimine in Molecular mass found bypotentiometric dosage in cm of ethyl alcohol, while keeping thetemperature methylisobutylketone by perchloric acid 224. of the reactionmixture in the vicinity of C. When the reaction is finished, the mixtureis neutralized with Analysis Calculated for Found acetic acid and thenfiltered under a nitrogen atmo- 5 u u S v sphere. 1.1 g of the abovediphenylamine leucoderiva- N% tive is obtained which, after washing inwater and drying under a vacuum, exhibits a melting point of 1 10C.EXAMPLE 4 Molecular mass calculated for C H N O 286.2-acetylamino-Lhydroxy-S-methyl-4'-amino-2'- Molecular mass found bypotentiometric dosage in 10 methoxy-S'-methyl-diphenylamine is preparedin acacetic acid by perchloric acid 290. cordance with the followingreaction:

. NHCOCH H N 1 N OCH l-l 'N Analysis Calculated for Found 3 To 200 cm ofa normal NaOH solution containing N9; "S 979 978 0.1 mole (21 g) ofsodium hydrosulfite there is added,

little by little, with stirring and under a nitrogen atmosphere, 0.032mole (9.5 g) of N-[(4'-amino-2"- EXAMPLE 3 methoxy-5'-methyl)phenyl]3-acetyIamino-6-methylbenzoquinoneimine in solution in cm of ethylalcohol, while keeping the temperature of the reaction mix-2-amino-4-hydroxy-5-methyl-4-amin ture in the vicinity of 30C. When thereduction reacdiphenylamine is prepared in accordance i the f tion isfinished, acetic acid is added until a pH of about lowing reaction: 7 isObtained. 8.8 g of the above diphenylamine H N N O S O Na 2H O CH NH 3 HN NH To 750 cm of a normal NaOH solution containing leucoderivative isfiltered which, after washing in water 0.47 mole (100 g) of sodiumhydrosulfite there is and drying undera vacuum, exhibits a melting pointof added, little by little, with stirring and under a nitrogen 233C.

atmosphere, 0.2 mole (45.4 g) of N-[(4- I Molecular'mass calculated forC H N O 315. amino)phenyl]5-amino2-methyl-benzoquinoneimine "Molecularmass found by potentiometric dosage in in solution in 250 cm of ethylalcohol, while keeping a i m dium by p rchloric acid 322.

the temperature of the reaction mixture in the vicinity AnalysisCalculmed f pound of 30C. When the reduction is finished, acetic acid isH M Q H added until a pH of about 7 is obtained. 44 g of the 13-33 abovediphenylamine leucoderivative is obtained and EXAMPLE 5 filtered undernitrogen. After washing the leucoderiva- 6:

tive in water and drying it undera vacuum, it exhibited Themonohydrochloride, monohydrate of 2-amino-4- a melting point of 177C.hydroxy-5-methyl-4-hydroxy-diphenylamine is pre- MOlBCUlaf massCalculated for 13 l5 3 pared in accordance with the following reaction:

l'lO

0.13 mole.(30 g) of N-[(4'-hydroxy)phenyl] 5-amino-2-methyl-benzoquinoneimine is dissolved in a hydroxy-diphenylamineis prepared in accordance with the following reaction:

H Y NR H Nl-l OH 0.01 mole (2.56 g) of N-[4-hydroxy-3',5'-

liter of 0.5N NaOH solution. Little by little, there is added thereto,with stirring and under a nitrogen atmo sphere, 0.25 mole (52 g) ofsodium hydro sulfite, while keeping the temperature of the mixture inthe vicinity of 30C. When the reduction is finished, acetic acid isadded until a pH close to neutrality is obtained. The resultingleucoderivative is filtered under nitrogen and is carefully washed withwater. It is then converted into2-amino-4-hydroxy-5-methyl-4'-hydroxydiphenylamine monohydrochloride,monohydrate b treatment with 2N hydrochloric acid. This product, afterrecrystallization in water, melts with decomposition at 144C.

Molecular mass calculated for C H N O HCL,

Molecular mass found by potentiometeric dosage in an aqueous medium witha soda solution -f 283.

EXAMPLE 6 I 2-amino-4-hydroxy-5-methyl-3 ,5 '-dimethyl-4'-crystallization in benzene, it exhibited a melting point of 167C.

Molecular mass calculated for C -J-I N O 258. Molecular mass found bypotentiometric dosage in methylisobutylketone by perchloric acid 263.

Calculated for Found CISHIMNZOIS l0.85

Analysis EXAMPLE 7 A hair dye composition is prepared as follows:

The diphenylamine leucodcrivative of Example 3 ().l5 gHydroxyethylcellulose 2 g Triethanolamine sufficient for pH Watersufficient for [00 g Gray hair is impregnated with this hair dyecomposition and after minutes exposure to the air, the hair is rinsed,then shampooed. A graycoloring with lilac glints is imparted thereto.

EXAMPLE 8 A hair dye composition is prepared as follows:

The diphenylamine leucoderivative of Example 2 0.05 gHydroxyethylcellulose 2 g Tricthanolamine sufficient for pH l0 Watersufficient for 100 g Bleached hair is impregnated with this hair dyecomposition and after 20 minutes exposure to the air, followed byrinsing and shampooing, a periwinkle blue coloring is imparted thereto.

EXAMPLE 9 The following hair dye composition is prepared:

The diphenylamine leucoderivative of Example 5 0.2 g Ethylene diaminetetraacetic acid 0.3 g Ammonium thioglycolate 0.5 g Ammonia sufiicientfor pH 8 Water sufficient for 100 g Gray hair is impregnated with thishair dye composition and after 20 minutes exposure to the air, the hairis rinsed and shampooed. A very clear chestnut coloring is impartedthereto.

EXAMPLE 10 A hair dye composition is prepared as follows:

The diphenylamine leucoderivative of Example I 0.03 gHydroxyethylcellulose 2 g Triethanolamine sufficient for pH l0 Watersufficient for 100 g Bleached hair is impregnated with this hair dyecomposition and after twenty minutes exposure to the air, the hair isrinsed and then shampooed. A platinum coloring with blue glints isimparted thereto.

' EXAMPLE 11 A hair dye composition is prepared as follows:

The diphenylamine leucoderivative of Example 6 0.2 gHydroxyethylcellulose 2 g Triethanolamine sufficient for pH 9 Watersufficient for 100 g Bleached hair is impregnated with this hair dyecomposition and after twenty minutes exposure to the air, the hair isrinsed and then shampooed. A clear golden copper coloring is impartedthereto.

EXAMPLE 1 2 A hair dye composition is prepared as follows:

The diphenylamine leucoderivative of Example 5 0.4 gN,N-4-dimethylamine-2'-4'-diamino-5- methyl-diphenylaminetrihydrochloride,

monohydrate 0.] g Ammonia sufiicient for pH 1 1 Water sufficient for [00cm EXAMPLE 1 3 A hair dye composition is prepared as follows:

The diphenylamine leucoderivative of Example 4 0.04 g 4hydroxy2,4'-diamino-5 -methoxydiphenylamine dihydrochloride,

monohydrate ()06 g Ammonia sufficient for pH 1 1 Water suflicient for100 g Gray hair is impregnated with this hair dye composition and aftertwenty minutes exposure to the air, followed by rinsing and shampooing,a very clear plum coloring with iridescent glints is obtained.

EXAMPLE 14 A hair-setting lotion is prepared as follows:

The diphenylamine leucoderivative of Example 6 (ll g Crotonic acid-vinylacetate copolymer 2 g Ethanol, 95 titer sufiicient for 50Triethanolamine sufficient for pH 9 Water sufficent for 100 g Thiscomposition applied as a hair-setting solution to bleached hair, givesit a tea rose shade.

EXAMPLE 1 5 A hair-setting solution is prepared as follows:

The diphenylamine leucoderivative of Example 6 0.08 g4-hydroxy-N,N-4'-dimethylaminodiphenylamine 0.02 g Crotonic acid-vinylacetate copolymer 2 g Ethanol, 95 titer, sufficient for 50Triethanolamine sufficient for pH 9 Water sufficient for 100 g Thiscomposition, appliedas a hair-setting lotion to bleached hair, gives ita very clear copper shade.

EXAMPLE 16 A hair-setting lotion is prepared as follows:

The diphenylamine leucoderivative of Example 3 0.1 g Crotonic acidvinylacetate copolymer 2 g Ethanol, 95 titer. sufficient for 50;Triethanola.mine sufficient for pH 9 Water sufficient for 100 g Thiscomposition, applied as a hair-setting lotion to bleached hair, gives ita clear violet shade.

EXAMPLE 17 A hair-setting lotion is prepared as follows:

The diphenylamine leucoderivative of Example 3 0.05 g Crotonicacid-vinyl acetate copolymer 2 g Ethanol, titer sufficient for 50Triethanolamine sufiicient for pH 9 Water sufiicient for g Thiscomposition, applied to gray hair as a hairsetting lotion, gives it abeige coloring with violet glints.

EXAMPLE l8 A hair-setting lotion is prepared as follows:

The diphenylamine leucodcrivative of Example 3 005 g 5 Crotonicacid-vinyl acetate copolymer 2 g Ethanol, 95 titer, sufficient for 50Triethanolamine sufficient for pH 7 Water sufficient for 100 g Thiscomposition, applied as a hair-setting lotion to bleached hair, gives ita clear beige shade with salmon glints.

EXAMPLE 1 9 A hair-setting lotion is prepared as follows:

The diphcnylamine leucoderivativc of Example 4 0.05 g

Crotonic acid-vinyl acetate copolymer 2 g Ethanol, 95 titer, sufficientfor 50 Triethanolamine sufficient for pH 7 Water sufficient for 100 gThis composition, applied to bleached hair as a hairsetting lotion,gives it a clear silvered gray shade. .25

EXAMPLE 20 A hairsetting lotion is prepared as follows:

The diphenylamine leucoderivative of Example 4 0.025 g4-hydrQxy-2,4'-diamino-5'-methoxydiphenylamine trihydrochloride,

monohydrate 0.025 g Crotonic acid-vinyl acetate Copolymer 2 g Ethanol,95 titer, sufficient for Triethanolamine sufficient for pH 9 35 Watersufficient for I00 g This composition, applied to bleached hair as ahairsetting lotion, gives it a clear beige shade with pearl glints. 4O

EXAMPLE 21 A hair-setting lotion is prepared as follows:

Ethylene diamine tetraacetic acid 2 g Ammonia sufficient for pH 10.5Water sufficient for 100 g Bleached hair is impregnated with this hairdye solution. After 20 minutes of exposure to the air, the hair isrinsed, then shampooed. A cyclamen shade is obtained.

EXAMPLE 23 A hair-setting lotion is prepared as follows:

The diphenylarnine leucodcrivative of Example I Crotonic acid-vinylacetate copolymer 2 g Ethanol, titer, sufficient for 50 Triethanolaminesufiicient for pH 9 Water sufficient for I00 g This composition appliedto bleached hair as a hairsetting lotion gives it a silver gray shadewith lavender glints.

EXAMPLE 24 A hair-setting lotion is prepared as follows:

The diphcnylamine lcucoderivat ive of Example 2 0.05 g Crotonicacid-vinyl acetate copolymer 2 g Ethanol, 95 titer, sufficient for 50Triethanoalmine sufficient for pH 9 Water sufiicient for g Thiscomposition, applied to bleached hair as a hairsetting lotion, gives ita gray tint with blue green glints.

EXAMPLE 25 A hair-setting lotion is prepared as follows:

The diphenylamine leucoderivative of Example 6 0.02 g Crotonicacid-vinyl acetate copolymer 2 g Ethanol, 95 titer, sufficient for 50Triethanolamine sufficient for pH 9 Water sufficient for 100 g Thiscomposition applied to bleached hair as a hairsetting lotion, gives it agolden apricot tint.

EXAMPLE 26 A hair dye composition is prepared as follows:

The diphenylamine leucoderivative of Example 2 0| gHydroxyethylcellulose l g Triethanolamine sufficient for pH 10 20 volumehydrogen peroxide 50 cm" Water sufiicient for lOO g Gray hair isimpregnated with this hair dye composition and after 20 minutes the hairis rinsed and then shampooed. A slate gray coloring is imparted thereto.

EXAMPLE 27 A hair dye composition is prepared as follows:

The diphenylamine leucoderivative of Example 6 0.025 g4-hydroxy-N,N-4'-dimethylamino- V diphenylamine 0.l gHydroxyethylcellulose l g Triethanolamine sufficient for pH I0 20 volumehydrogen peroxide 50 cm Water sufficient for 100 g Gray hair isimpregnated with this hair dye composition and after 20 minutes the hairis rinsed and then shampooed. A verdigris shade is imparted thereto.

What is claimed is:

l. A keratinous fiber dyeing composition consisting essentially of anaqueous solution of a member selected from the group consisting of (a) adiphenylamine of the formula wherein Y represents a member selected fromthe group consisting of hydroxy and amino, R and R each independently,represent a member selected from the group consisting of hydrogen,halogen, lower alkyl containing l-4 carbon atoms, lower alkoxycontaining l-4 carbon atoms, a ureido residue and NHCOR wherein Rrepresents lower alkyl containing l-4 carbon atoms, R represents amember selected from the group consisting of hydrogen, halogen, loweralkyl containing l-4 carbon atoms, lower alkoxy containing l-4 carbonatoms, a ureido residue -NHCOR wherein R represents lower alkylcontaining l-4 carbon atoms and -1 ll-lR wherein R represents a memberselected from the group consisting of hydrogen, lower alkyl containing1-4 carbon atoms, lower hydroxy alkyl containing 1-4 carbon atoms andcarbamylmethyl, with the proviso that when R is -NHR R is not hydrogen,R R R, and R each represent a member selected from the group consistingof hydrogen, halogen, lower alkyl containing 1-4 carbon atoms and loweralkoxy containing l-4 carbon atoms, with the proviso that when Y ishydroxy, R is not hydrogen, halogen, lower alkyl containing l-4 carbonatoms or lower alkoxy containing 1-4 carbon atoms, and that when Y isamino, at least two of R R and R are other than hydrogen and R is nothydrogen when R.,, R R and R are all hydrogen; and (b) the hydrochlorideof the diphenylamine of (a), said diphenylamine being present in amountsof 0.01 to 0.1 percent by weight of said composition and saidcomposition having a pH between 7 and 10.

2. The composition of claim 1 wherein the diphenylamine is selected fromthe group consisting of 1 3 ,5-dimethyl-4-hydroxy-4 '-amino-3 ',5'-dimethyl- 2'-methoxy-diphenylamine;

2. 3 ,6-dimethyl-4-hydroxy-4 '-amino-3 ',5 '-dimethyl- 2-met hoxydiphenylamine;

3. 2-amino-4hydroxy-5-methyl-4'-aminodiphenylamine:

4. 2-acetylamino-4-hydroxy-5-methyl-4 -amino-2 methoxy-S-methyl-diphenylamine;

5. the monohydrochloride, monohydrate of 2-amino-4-hydroxy-5-methyl-4-hydroxy-diphenylamine; and

6. 2-amino-4-hydroxy-5 -methyl-3 ,5 '-dimethy1-4 hydroxy-diphenylamine.

3. A hair-setting lotion composition consisting essentially of anaqueous solution of a lower alkanol present in amounts ranging fromabout to 50 percent by weight of said composition, a film-forming resinand a member selected from the group consisting of (a) a diphenylamineof the formula wherein Y represents a member selected from the groupconsisting of hydroxy and amino, R and R each independently, represent amember selected from the group consisting of hydrogen, halogen, loweralkyl containing 1-4 carbon atoms, lower alkoxy containing 1-4 carbonatoms, a ureido residue and 1 ll-lCOR wherein R represents lower alkylcontaining 1-4 carbon atoms, R represents a member selected from thegroup consisting of hydrogen, halogen, lower alkyl containing l-4 carbonatoms, lower alkoxy containing l-4 carbon atoms, a ureido residue andNl-lCOR wherein R represents lower alkyl containing 1-4 carbon atoms and-NHR wherein R represents a member selected from the group consisting ofhydrogen, lower alkyl containing 1-4 carbon atoms, lower hydroxy alkylcontaining l-4 carbon atoms and carbamylmethyl, R R R and R eachrepresent a member selected from the group consisting of hydrogen,halogen, lower alkyl containing l-4 carbon atoms and lower alkoxycontaining l-4 carbon atoms and (b) the hydrochloride of thediphenylamine of (a), said diphenylamine being present in amounts of0.01 to 0.1% by weight of the total composition, said film forming resinbeing selected from the group consisting of polyvinylpyrrolidone havinga molecular weight ranging from about 10,000 to 700,000 and copolymer ofvinylpyrrolidone-vinyl acetate wherein the ratio of VP to VA rangesbetween 50-70:- 50-30 and being present in amounts of 1-3% by weight ofsaid composition and said composition having a pH between 7 and 10.

4. The composition of claim 3 wherein the pH ranges between 7-9.

5. The composition of claim 3 wherein the lower alkanol is selected fromthe group consisting of ethanol and isopropanol.

6. The composition of claim 3 wherein the diphenylamine is selected fromthe group consisting of 1 3,5-dimethyl-4 hydroxy-4'-amino-3 ',5'-dimethyl- 2-methoxy-diphenylamine;

2. 3 ,6-dimethyl-4-hydroxy-4-amino-3 ',5 '-dimethyl-2'-methoxy-diphenylamine;

3. 2-amino-4-hydroxy-5-methyl-4'-a.minodiphenylamine;

4. 2-acetylamino-4-hydroxy-5-methyl-4 arnino-2 methoxy-S'-methyl-dipheny1amine;

5. the monohydrochloride, monohydrate of 2-amino-4-hydroxy-5-methyl-4'-hydroxy-diphenylamine; and

6. 2-amino-4-hydroxy-5-methyl-3 ,5 '-dimethyl-4 hydroxy-diphenylamine.

1. A KERATINOUS FIBER DYEING COMPOSITION CONSISTING ESSENTIALLY OF ANAQUEOUS SOLUTION OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF (A) ADIPHENYLAMINE OF THE FORMULA
 2. The composition of claim 1 wherein thediphenylamine is selected from the group consisting of 2.3,6-dimethyl-4-hydroxy-4''-amino-3'',5''-dimethyl-2''-methoxy-diphenylamine;2.3,6-dimethyl-4-hydroxy-4''-amino-3'',5''-dimethyl-2''-methoxy-diphenylamine;3. 2-amino-4-hydroxy-5-methyl-4''-amino-diphenylamine; 3.2-amino-4-hydroxy-5-methyl-4''-amino-diphenylamine;
 3. A hair-settinglotion composition consisting essentially of an aqueous solution of alower alkanol present in amounts ranging from about 20 to 50 percent byweight of said composition, a film-forming resin and a member selectedfrom the group consisting of (a) a diphenylamine of the formula 4.2-acetylamino-4-hydroxy-5-methyl-4''-amino-2''-methoxy-5''-methyl-diphenylamine; 4.2-acetylamino-4-hydroxy-5-methyl-4''-amino-2''-methoxy-5''-methyl-diphenylamine;
 4. The composition of claim 3 wherein the pH rangesbetween 7-9.
 5. The composition of claim 3 wherein the lower alkanol isselected from the group consisting of ethanol and isopropanol.
 5. themonohydrochloride, monohydrate of2-amino-4-hydroxy-5-methyl-4''-hydroxy-diphenylamine; and
 5. themonohydrochloride, monohydrate of2-amino-4-hydroxy-5-methyl-4''-hydroxy-diphenylamine; and 6.2-amino-4-hydroxy-5-methyl-3'',5''-dimethyl-4''-hydroxy-diphenylamine.6.2-amino-4-hydroxy-5-methyl-3'',5''-dimethyl-4''-hydroxy-diphenylamine.6. The composition of claim 3 wherein the diphenYlamine is selected fromthe group consisting of